Alkyl-arylsulphaminonaphthol sulphonic acid azo dyes



Patented Oct. 12, 1926.

UNITED STATES PATVENTIOFFICEO.

l 'WILHELM NEELMEIER, OF LEVERKUSEN, NEAR COLOGNE, AND THEODOR NOGKEN,

OF WIESDORF, NEAR COLOGNE, GERMANY, ASSIGNORS TO GRASSELLI DYESTUFI CORPORATION,'OF NEW YORK, N. Y., A CORYORATION OF DELAWARE.

ALKYL-ARYLSIl'I ZBHAMINONAPHTHOIa sunrnomc ACID AZO DYES.

NoiDrawing. Application filed February 3, 1925, Serial No. 6,658, and in Germany February 13, 1924.

We have invented new and useful improvements in azo dyestuffs of which the following is a specification.

Our invention consists in the use as coupling components of amino-naphthol-sulphonic acids substitutedin a certain marrner in the amino group and in the new azo dyestuffs obtained by this process.

The substitution of the amino groups in azo-dye components is generally accompanied by increased fastness properties, deeper shades or other valuable modifications of the characteristics of the colors. After the first attempts in this direction as shown for instance in dyestuffs of the type benzol azo F acetylamino 8-naphthol-3-6-disulphonate of sodium more complicated acidylamino dyestuffs have been produced, we might only mention the important grou of urea colors, the 2-benzoylamino-5-napht ol- 7-sulphonic acid colors and as a more recent development in this line the dyestuffs in which the amino group is substituted by an aryl-sulpho radical. According to our in vention we are now going one step further in this substitution and are also replacing the second hydrogen atom in the amino group of azo dye components. The coupling components which we now use are of the type alkyl-arylsulph amino naphthol sulphonic aclds:

. noasn SOzY in which formula X is an alkyl group such as CH 0 H, C,H,OH, 011 0 11 etc. and Y an aryl group. such as G l-I G ITLOH C,H,.OH.GOOH, etc. and n .is the numeral 1 or 2.

Compared with the corresponding colors from aryl-sulphamino-naphthol-sul honic acids our new products are distinguis ed by still better fastness properties, especially increased fastness to chlorine, which is quite valuable when these dyestuffs are used for calico printing. The shades of our new products are more'on the yellowishside of the color scale, which allows ofa wider range of tints obtainable. from the same class of dyestufls having otherwise similar dyeing properties. The use 'of aryl-sulpho substituted amines as in the prior art is in itself of a technical advanta e as it allows to introduce into the molecule radicals pro- I fluence on the shade, solubility, et-c., of our new dyestuffs, we have found that )the illcreased fastness and change, of coloristic properties is maintained in all cases where the second hydrogen atom in the aryl-sulphamino group is replaced by an alkyl group as specified above. For the purpose of our invention it is therefore i material if the alkyl arylsulphamino nap thol sulphonic acids are coupled with the diazo compounds from mononuclear amines or from aminoazo derivatives or other morecomplicated amlnes.

Our new dyestuffs dye wool generally from red to blue fast shades; when using for instance alkyl-salicyl-sulphamino-naphthol-sulphonic acids as coupling components the products dye wool after chromed similar red to blue -fast shades; they can also be.

used in conjunction with chrome acetate for cotton printing and the same shades, being exceedingly.fast to chlorine and washing, are obtained.

In order to illustrate our invention further, the following examples are given, the parts being by weight.

We wish it, however, to be understood that our invention is not limited tothese specific examples nor to the conditions given therein;

Example "IF-391 parts :l-ethylamino-S- naphtho1-3-6-di-sulphonate of sodium are dissolved in 2000 parts of water; 136 parts of crystallized sodium acetate and 190.5 parts of p-toluol-sulphochloride are added and the reaction carried out for several hours at 7080 C. The completion of the reaction is shown when a sample of the solution does not react any more with nitrous acid. Should a test with nitrite of sodium in acid solution still show unreacted ethylamino-naphthol-sulphonic acid more sodium acetate and toluol-sulphochloride is added, until the reaction is complete. The obtained 1 ethyl p toluolsulphamino 8 naphthol-3-6-disulphonate of sodium is exceedingly soluble in water and it is difiicult to isolate same in pure form. The solution obtained as described can, however, be used as such.

137 parts of o-phenetidine are now diazotized in the usual manner and the diazo solution is run into the solution of l-ethylp toluolsulphamino 8 naphth-0l-3-6-disulphonate of sodium obtained as above and cooled to about 0 with ice, adding 106 parts of soda ash. The coupling is finished in a few hours. The dyestufi' is thrown out of solution by the addition of salt, filtered and dried. It is in form of its sodium salt a dark red powder, soluble in water with a reddish blue color, soluble in concentrated sulphuric acid with a violet-red color; it dyes wool very level, clear, bluish red shades, fast to milling. In its free form the dyestuif has most probably the formula:

OCH CIHB Ho O N=N: j

SO|H Hogs Example 2.253 parts of 2-methylainin0- S-naphthol-G-sulphomc acid are dissolved aH 001E! Q Q OaH a It is bronz in water with a bluish Viole color, soluble 1n concentrated sulphuric acid with a blue color. It dyes wool in an acid bath bluish vlolet shades, which are not much changed .by afterchroming; printed on cotton with bluish violet powder, soluble eoavve and neutralized in 2000 parts of water by the addition of 53 parts soda ash. 136 parts of crystallized sodium acetate are now dissolved in this solution and 236.5 parts of salicyl-sulphochloride gradually introduced within one hour. As the. condensation proceeds the reaction product separates as fine. colorless crystals. The reaction is complete after about 8 hours stirring at room ternperature; if necessary, a small excess of salicylsulphochloride and sodium acetate is added. The 2-methyl-salicylsulphaniino-8- naphthol'6-sulphonate of sodium forms small, colorless leaflets, easily soluble in hot water. The product as obtained is used in the preparation of our new azo dyestuffs.

297 parts of aniline-Q-5-disulphonate of so dium are now diaz otized in the usual manner. The diazo solution is run into a solution of 187.5 parts 3-amino-4-cresol ethylether in 1000 parts water. The acidity of the coupling reaction is neutralized with sodium acetate, the combination is complete after 24 hours, it is acidified, salted out hot and filtered. The monoazo color so obtained is dissolved in 3000 parts of soda ash solution,

69 parts nitrite of sodium added and the whole run into 250 parts muriatic acid 19 Be. and 500 parts water cooled to 10. This second diazotation is finished when a sample made alkaline does not turn purple after addition of mineral acid.

The diazo solution so obtained is quickly introduced into a solution of 475 parts of 2- methyl-salicyl-sulphamino-8-naplithol-6-sulphonate of sodium prepared as above, dissolved in 2000 parts of water with 175 parts of soda ash. The combination proceeds rapidly. The dyestufl is salted out, filtered oil and dried. In its free form the dyestufi" has most probably the formula:

2. The process of producing new azo dyestuffs which consists in combining; diazotized aromatic amines with l-alkyl-arylsulphamino-8-naphthol-3-6-disulphonie acids substantially as described.

3. The process of producing a new azo dyestuff which consists in-combining diazotized o-phenetidine with l-ethyL aratoluolsulphamino-8-naphthol-3-6-disulp onic acid substantially as described.

4.-. As new products the azo dyestuffs which are substantially identical with the dyestuiis obtainable by combining diazotized aromatic amines with alkyl-arylsulphaminonaphthol-sulphonic acids, which dyestuffs water with from red or blue color and d e- I ing wool from an acid bath from red to b ue fast shades.

5. As new products the azo dyestufl's which are substantially identical with the dyestufi's obtainable b combinin 'diazotized aromatic amines with l-alky -arylsulphamino 8 naphthol 3 6 disulphomc acids, which dyestufi's are dark red powders, sol-' uble in water with from red to blue colors, soluble in concentrated sulphuric acid with a violet-red color and dyeing wool in an acid bath from red toblue fast shades.

6. As a new product the azo dyestufi which is substantially identical with the dyestufi obtainable by combining diazotized' 0-- phenetidine with l-ethyl-paratoluolsulphamino-8-naphthol-3-6-disulphonic acid having most probably the formula:

, cm G H01 IH which dyestufi is a dark red powder, soluble in water with a bluish red color, soluble in concentrated sulphuric acid with a violet- 30 red color and dyeing wool in an acid bath red, fast shades.

In testimony whereof we have hereunto set .Our hands.

WILHELM NEELMEIEB. THEODOR NOCKEN. 

